This document outlines the course roadmap for an organometallic chemistry course. It will cover the basics of organometallic chemistry including electron counting, main group and transition metal chemistry, and common reaction types like insertion, elimination, and oxidative addition/reductive elimination. As an example, it will discuss the industrial Monsanto process for producing acetic acid catalytically using a rhodium complex and methanol. Students will learn to understand and explain organometallic reactions and current research papers.

1. Organometallic Chemistry
between organic and inorganic
Peter H.M. Budzelaar

2. Organometallic Chemistry2
Course Roadmap
• A real example: the Monsanto Acetic Acid process
• Introduction: what is organometallic chemistry, and why should you care?
• Electron counting: the basis for understanding structure and reactivity
• An overview of Main-group and Transition metal chemistry
• Main group metal chemistry and "Umpolung"
• Intermezzo: characterization of organometallic compounds
• Transition metal chemistry: overview of common ligands
• Ligand substitution
• Insertion and elimination
• Oxidative insertion and reductive elimination
• More exotic steps
• Your own presentations
• Applications in catalysis

3. Organometallic Chemistry3
Example: Acetic Acid synthesis
Acetic acid is an important industrial chemical.
The traditional synthesis uses bio-oxidation of ethanol obtained via
fermentation:
C6H12O6 → 2 C2H5OH + 2 CO2
C2H5OH + O2 → CH3COOH + H2O
This is not a clean and efficient process!
Industrial acetic acid synthesis:
CH3OH + CO → CH3COOH
Catalyzed by a rhodium complex.

4. Organometallic Chemistry4
Acetic Acid synthesis
Moderately complex
catalytic cycle:
H2O
HI CH3OH
CH3I
CH3COOH
CH3COI
Rh(CO)2I2
-
MeRh(CO)2I3
-
MeCORh(CO)I3
-
MeCORh(CO)2I3
-
CO

5. Organometallic Chemistry5
Acetic Acid synthesis
This cycle is known
in considerable detail:
To understand it,
you need to be familiar
with electron counting
and common
reaction types
CO
Rh(CO) I2 2
-
MeRh(CO) I2 3
-
MeCORh(CO) I2 3
-
MeCORh(CO)I3
-
CH I3
CH COI3
CH COOH3
H O2
HI CH OH3
RhI
16 e
RhIII
18 e
RhIII
16 e
RhIII
18 e
oxidative
addition
insertion
reductive
elimination
ligand
binding

6. Organometallic Chemistry6
What is organometallic chemistry ?
Strictly speaking, the chemistry of compounds containing
at least one metal-carbon bond.
Metal hydrides are often included, H being considered as the
"smallest organic group" (as in propyl, ethyl, methyl, hydride).
Metal-carbon bonds are often formed temporarily or potentially,
so in practice many compounds are included
that do not actually contain metal-carbon bonds.
(Ph3P)3RhCl
H2
O
OMe
Li
O
OMe
Li

7. Organometallic Chemistry7
Why should you care ?
Organometallic chemistry is the basis of homogeneous catalysis,
which is the method of choice for clean and efficient synthesis of
fine chemicals, pharmaceuticals and many larger-scale
chemicals.
Many plastics (polythene, polypropene, butadiene rubber, ...)
and detergents are made via organometallic catalysis.
Organometallic chemistry is also the basis for understanding
important steps in heterogeneous catalysis reactions such as
olefin hydrogenation and CO oxidation.
Organometallic compounds are used on a large scale as
precursors for generation of semiconductors (AlN, GaAs,
etc).
Silicone rubbers are one of the few classes of organometallic
compounds used as "final products".

8. Organometallic Chemistry8
Course Objectives
By the end of this course, you should be able to:
• Make an educated guess about stability and reactivity of a given
compound, based on (a.o.) electron counting rules
• Propose reasonable mechanisms, based on "standard"
organometallic reaction steps, for many metal-catalyzed
reactions
• Use steric and electronic arguments to predict how changes in
reactants, metal or ligands affect the outcome of reactions
• Read a current research literature paper, understand and
explain its content and significance

9. Organometallic Chemistry9
Useful Background Knowledge
Organometallic chemistry (CHEM 4680) is a 4th
-year course
because it builds on:
• Organic chemistry: reaction mechanisms, primarily nucleophilic
and electrophilic attack
• Inorganic Chemistry: electronegativity; electron counting and
stability; properties of (transition) metals
• Physical chemistry: orbitals and MO theory; free energy,
enthalpy and entropy
You will (now and then) need this background to understand the
material or make assignments etc

10. Organometallic Chemistry9
Useful Background Knowledge
Organometallic chemistry (CHEM 4680) is a 4th
-year course
because it builds on:
• Organic chemistry: reaction mechanisms, primarily nucleophilic
and electrophilic attack
• Inorganic Chemistry: electronegativity; electron counting and
stability; properties of (transition) metals
• Physical chemistry: orbitals and MO theory; free energy,
enthalpy and entropy
You will (now and then) need this background to understand the
material or make assignments etc